Epoxidation of hexafluoropropylene

ABSTRACT

A PROCESS FOR THE EPOXIDATION OF HEXAFLUOROPROPYLENE WHICH COMPRISES (A) ACTIVATING A COMPOSITION CONSISTING ESSENTIALLY OF SILICA BY CONTACTING IT WITH A MIXTURE OF OXYGEN AND HEXAFLUOROPROPYLENE AND/OR HEXAFLUOROPROPYLENE EPOXIDE AT FORM 175 TO 400*C. AND (B) CONTACTING THE ACTIVATED COMPOSITION WITH HEXAFLUOROPROPYLENE AND OXYGEN AT FROM 140 TO 280*C.

United States Patent ()lfice 3 775 438 EPOXIDATION or IiEXAFLUQRoPRoPYLENE Robert John Cavanaugh, Wilmington, DeL, assignor to E. I. du Pont de Nemours and Company, Wilmington, Del. No Drawing. Filed May 31, 1972, Ser. No. 258,360

Int. Cl. C07d 1/06 US. Cl. 260-348.5 R 8 Claims ABSTRACT OF THE DISCLOSURE This invention relates to the epoxidation of hexafluoropropylene. In particular, this invention relates to accomplishing the aforesaid epoxidation through the use of a'silica composition and oxygen.

The epoxide of hexafluoropropylene is known. Examples of processes for its preparation are reaction with oxygen in the presence of a silver catalyst, the use of a medium of alkaline hydrogen peroxide and a technique involving contacting the fiuorinated olefin with oxygen at superatmospheric pressure and elevated temperatures in an inert fluid diluent. An improved process was sought.

Such a process has been found. It is a process for the epoxidation of hexafluoropropylene which comprises (a) activating a'composition consisting essentially of silica by contacting it with a member selected from the group consisting of a mixture of oxygen and hexafluoropropylene, hexafluoropropylene epoxide, and mixtures thereof, at from 175 to 400 C., preferably from 200 to 280 C. and (b) contacting the activated composition with hexafluoropropylene and oxygen at from 140 to 280 C., preferably from 190 to 225 C.

The composition consisting essentially of silica is normally at least 60 percent by weight silica, preferably at least 95 percent by weight silica. Consisting essentially of as used throughout the specification and claims does not exclude unspecified materials which do not prevent the advantages of the invention from being realized. Examples of useful compositions are silica gel, soft glass (approximately 72 percent by weight Si 15 percent by weight Na 0, 9 percent by weight CaO, 3 percent by weight MgO, and 1 percent by weight A1 0 Pyrex Brand glass (Corning Glass Works, Corning, NY.) (approximately 80 percent by weight SiO 14 percent by weight B 0 4 percent by weight Na O, and 2 percent by weight A1 03), Vyc0r Brand glass (Corning Glass Works) (approximately 96 percent by weight SiO 3 percent by weight B 0 and 1 percent by weight other oxides), Pyroceram Brand Ceramic (Corning Glass Works), lithium alumino-silicate glass, macroporous silica beads Gordler silica carrier T-869 (Chemetron Corp., Girdler Div., Louisville, Ky.), and sand. Normally for better results the glasses are ground to at least a macropowder (10-30 mesh) before using in the process of this invention. However, this is not required. The silica beads, for example, cause the production of hexafluoropropylene epoxide without grinding. Silica gel is the preferred composition. Silica gel is normally at least 98 percent by weight silica and preferably has a surface area of at lest 80 meter /gram. Silica gels with surface areas of at least 200 meter /gram are most preferred.

The composition is normally activated by contacting it with oxygen and hexafluoropropylene and/ or hexafluoro- 3,775,438 Patented Nov. 27, 1973 propylene epoxide at from 175 to 400 C., preferably from 200 to 280 C. Activation is defined as improving the compositions capability of catalyzing the conversion of hexafluoropropylene and oxygen to hexafluoropropylene epoxide. The activation temperature and times are dependent on one another, the type of composition utilized and type of atmosphere used for activation. If there is a high temperature, the time to activate the composition is less whereas if the temperature is low, the time required for activation is longer. The time required for activation is normally from V: to 25 hours. With the preferred activation temperatures, the time required for activation is normally from 2 to 5 hours.

Some compositions are easily activated in an oxygen and hexafluoropropylene atmosphere while others are more readily activated in an atmosphere which also contains some hexafluoropropylene epoxide or which is substantially all hexafluoropropylene epoxide. The use of an atmosphere which contains some or all hexafluoro propylene epoxide is sometimes preceded or followed by the use of a mixture of hexafluoropropylene and oxygen. The oxygen can be in the form of air or other gas mixures normally containing at least 20 percent by volume oxygen with the remainder being gas which is inert to the reaction such as helium or carbon dioxide. A gas which is substantially all oxygen is preferred.

The process of this invention can be batch or continuous, the latter being preferred. In a continuous operation the hexafluoropropylene and oxygen are passed over a bed of the composition which can be in a fixed or fluidized form. In the fluidized bed, there is normally continual addition and removal of the composition from the bed. Thus, continued activation of new composition is taking place followed by the epoxidation of the hexafluoropropylene over the composition after such activation. Alternatively, the composition can be activated (step (a)) prior to its addition to the bed.

The molar ratio of the hexafluoropropylene to oxygen as fed to the reactor in which the epoxidation is to take place is normally from 1:5 to 15:1, preferably from 2:1 to 8:1 in both steps (a) and (b) of the process of this invention. The statements above relating to step (a) concerning the forms of the oxygen also apply to step (b).

In the process of the present invention, yields of up to about percent and above can be obtained employing some of the compositions. The conversions normally are about 10 to 40 percent. Conversion as used throughout is defined as the percentage amount of the hexafluoropropylene converted to compounds other than hexafluoropropylene specifically, to CO CO CF COF, and HFPO. The percentage yield of hexafluoropropylene epoxide is times the moles of hexafluoropropylene converted to hexafluoropropylene epoxide divided by the moles of hexafluoropropylene consumed. The percentage yields of the other compounds are calculated similarly.

The pressure at which the process of this invention is operated depends on the temperature involved. Atmospheric pressure is normally utilized; snperatmospheric pressure, normally not above about 3 atmospheres, can be utilized but these higher pressures are generally used when the lower temperatures are being maintained. Some compositions produce lower conversions at the lower temperatures, and require higher temperatures or the use of pressure for the preferred yields and conversions. Superatmospheric pressurecan be used in both step (a) and step (b), for instance, when a continuous process is utilized, but can be limited to only step (b).

The process of this invention generally produces hexafluoropropylene epoxide in good yields and conversions for 10-80 hours. However, after this period, significant amounts of hexafiuoroacetone are produced rather than the hexafluoropropylene epoxide. It has been found that this can be prevented by having present from 0.5 to 3 height in the feed and exit streams for a given sainple mole percent water, based upon total reactants, i.e., hexasize. The yield of hexafluoropropylene epoxide was calfluoropropylene and oxygen. Addition of water increases culated on the basis of peak height corrected for the difcomposition life significantly. Normally, the addition of ference in thermoconductivity. Water is used in step (b) but it can also be used in step 5 (a). If the technique of adding water is not utilized, the TABLE 3 aged composition can be regenerated by passing steam Flow rates, ml./ Convcrover it followed by step (a) of the process of this invenjgg Percent yield tion. HF? 02 HFP HFPO co The hexafiuoropropylene epoxide can be separated from 20 m the outlet stream of the reactor in the process of this in- 20 "6 "6 "6 vention by scrubbing and extractive distillation. g8 18 0 0 Hexafluoropropylene epoxide is useful as an intermedi- 2o 10 1:111:11:IIIIIII: ate for preparing other intermediates such as perfiuoro- 38 lg 55 0 vinyl ethers or high temperature resistant fluids. The ethers 1o "55 "s are useful in the preparation of ion exchange membranes, 38 {g 54 7 25 mechanical polymers, and elastomers. 20 10 "5i "2i "25 The following examples are meant to illustrate but not 28 i8 57 h 23 to limit the invention. All percentages are molar unless 20 10 "5i "5i "55 otherwise specified. In the examples HEP is hexafluoro- 55 34 23 propylene; HFPO is hexafiuoropropylene epoxide; and PAP is perfiuoroacetyl fluoride. EXAMPLE 1V EXAMPLE I Ninety cc. of Pyroceram lithium alumino-silicate glass A 6, outside diameter stainless steel tube in the (Coming Glass Works, J Was form of a coil was charged with 90 ml. of Davison silica 0 rg d t a 6 long, outs1de diameter, stainless steel gel Grade 2 (Davison Div Grace, Inc 1 coil immersed in a silicone oil bath. The composition bed more, Md) h Coil was placed in a Silicone oil bath was heated at 200 C. for 75 minutes under a stream of heated to 200 C. at 10:00 and the stream of 20 ml./ min. 20 hexahhoropropylehe and 'h Y' of hexafluoropropylene and 10 ml./min. of oxygen was The temperature s othen lnereasedfo 240 and introduced into the tube. Table 1 below indicates the fluctuated from thatfo 301 Pp y data obtained for the rest of the run. Analysis was by gas T e w substantlally no conv r l n f HFP. At ha chromatography. time the stream of hexafiuoropropylene and oxygen was TABLE 1 Flow rates, Con- Bed ml./min. version, Percent yield temp, percent Time C. HFP Oz HFP HFPO CO3 COFz PAF 11 201 20 10 5 e7 0 s3 0 14:30 202 20 10 7 70 o 21 0 Heated as is overnight 08:35 20a 20 10 7a 4 5 17 EXAMPLE II 45 replaced by a stream of hexafluoropropylene epoxide.

The temperature was held at approximately 250 C. for to a outside diameter stainless steel tube in the 30 minutes while the bed was held under a stream of hexform o f a coil. The coil was immersed in a silicone oil ahhoropropylehe epoxide (2O mummy At the end of bath. The coil was heated for 2% hours at 240 C. under the 30 minutes the hexahuoroPmPyhme ePoxide Stream a stream of 20 ml./min. hexafluoropropylene and 10 ml./ Was replaced y a stfeam'of 20 hexafiuofopro' Ninety m1. of Davison silica gel, Grade 45, was charged min. oxygen. Table 2 depicts the data from the rest of the Py and 10 min. Y Q- The temperatufe was run. Analysis was by gas chromatography. lowered to 220 C. After 15 minutes the analysis of a TABLE 2 Flow rates, ConmL/min. version, Percent yield percent o HFP o, HFP HFPO 00, con, PAF

20 10 2s 2s 72 o 0 20 10 19 40 so 0 0 2o 10 1s 40 so 0 0 2o 10 20 45 o 0 EXAMPLE III sample from the exit stream of the coil indicated that the r 1 n hexafiuoropropylene conversionwas 66.1 percent, the A 1 long omslde dlameter quartz tube was hexafluoropropylene epoxide yield was 24.2 percent, the

charged with 90 ml. of Pyrex Brandglass P Glass yield of carbon dioxide'wa's 6.2 percent, the yield of car- Works, Corhlhg, ground to Pass a 40 mesh sleve' bonyl fluoride was 30.3 percent, the perfiuoroacetyl fiuoh tube Placed in a tube h f h heated Over ride yield was 39.3 percent, and there was a trace of hexmght hh a Stream of 20 mh/mm' hehum 9 afiuoroacetone. Analysis was by gas'chromatography. The temperature was recorded by means of a thermo- H couple placed in a well in the center of the catalyst bed. .IEXAMPLE V The-helium was turned off and a stream of 20 mL/min. v hevafiuoropropylene and 10 mL/min. oxygen was turned Approximately ninety ml. of silica .sand (granular) on Table 3 below indicates the data from the run. The (Fisher Scientific Company Pittsburgh, Pa.) were reactor exit stream was analyzed by gas chromatography. charged to a 6 long, outside diameter stainless steel "The conversion in this example was calculated by meascoil immersed in a silicone oil bath. Thebed was conuring the difference in the hexafluoropropylene peak tacted withastream of hexafluoropropylene (zo'ce/min.)

6 EXAMPLE VII A 6', outside diameter stainless steel tube was charged with 90 cc. of Davison silica gel, Grade 02. The tube was placed in a silicone oil bath maintained at 260 propylene (110 cc./m1n-), C. and a stream of mL/min. hexafluoropropylene and POXlde cc/mllh) and Oxygen 10 ml./min. oxygen was passed through the tube. After 2 The data from h l'emalndel' 0f the run minutes, gas chromatographic analysis of the reactor exit stream showed 13 percent of the hexafiuoropropylene TABLE 4 Flow rate, ConvermLImin. sion, Percent yield percent and oxygen (10 ccJmin.) for 2 /2 hours at 240 C., there was no conversion of HFP. Prior to such the silica bed had been heated overnight at 240 C. helium. The silica bed was then treated for minutes at from 24 0 to 223 C. under a stream of hexafluoro hexafluoropropylene e (10 cc./ min.)

is shown in Table 4. Analysis was by gas chromatography.

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likewise passed through the water saturator. The reactor was operated under these conditions for additional 39 /2 hours. The feed stream was then switched back to 20 ml./ min. hexafluoropropylene and 10 ml./min. oxygen and passed through the bubbling stone immersed in water. A needle valve at the exit of the reactor was then partially closed to allow the reaction to proceed under pressure. The results are shown in Table 6. Analysis was by gas chromatography.

I claim:

1. A process for the epoxidation of hexafiuoropropylene which comprises (a) activating a composition consisting essentially of silica by contacting it with a member selected from the group consisting of a mixture of oxygen and hexafiuoropropylene, hexafluoropropylene epoxide and mixtures thereof, at from 175 to 400 C. and (b) contacting the activated composition with hexafluoropropylene and oxygen at from 140 to 280 C.

2. The process of claim 1 in which step (a) is carried out for /2 to 25 hours.

3. The process of claim 1 in which step (a) is carried out at from 200 to 280 C.

4. The process of claim 1 in which step (b) is carried out at from 190 to 225 C.

5. The process of claim 1 whichis carried out atsuperatmospheric pressure. 7 1 I v 6. The process of claim 1 in which step (b) is carried out in the presence of water, said water being present to the extent of 0.5 to 3 mole percentofthe-itotal moles'of hexafiuoropropylene and oxygen contacted with the activated composition. v I

7. The process of claim 6 wherein the;composition consisting essentially of silica is silica gel.

8. The process of claim 7 in which step (a) is carried out at 200 to 280 C. and step (b) at 190 to 225- C. I

References Cited UNITED STATES PATENTS NORMA S. MILESTONE, Primary Examiner s. 01. X.R. 260-348.5 F 

